CN110092763A - A kind of preparation method of ultraviolet absorbing agent UV-328 - Google Patents
A kind of preparation method of ultraviolet absorbing agent UV-328 Download PDFInfo
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- CN110092763A CN110092763A CN201910455654.6A CN201910455654A CN110092763A CN 110092763 A CN110092763 A CN 110092763A CN 201910455654 A CN201910455654 A CN 201910455654A CN 110092763 A CN110092763 A CN 110092763A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
Abstract
The present invention provides the preparation methods of ultraviolet absorbing agent UV-328 a kind of, this method includes preparing 2- (bis- tertiary amyl phenyl of 2'- hydroxyl -3', 5'-) benzotriazole product through ammonification, diazotising, coupling, step reduction, two step reduction reactions and last handling process by o-nitrochlorobenzene.The present invention uses concentration that will generate diazonium salt through diazo-reaction with nitrite again after o-nitrochlorobenzene ammonification for 10%~25% ammonium hydroxide, the diazo-reaction under strong acid media without carrying out, and fully utilize the byproduct ammonium hydroxide of our company's existing procucts, three wastes low emission, and it is required at low cost；The reduction closed loop procedure of intermediate azo product uses 2 stage reduction methods, avoids strong reductant and azo double bond is directly reduced into amine, reduces impurity and generates, not only increases product purity, while improving product yield.
Description
Technical field
The present invention relates to substance synthesis technical field more particularly to a kind of preparation methods of ultraviolet absorbing agent UV-328.
Background technique
2- (bis- tertiary amyl phenyl of 2'- hydroxyl -3', 5'-) benzotriazole, be one is excellent light stabilizer kind,
Advantage is that performance is stable, toxicity is low, ultraviolet absorption ability is strong, and there is product name UV- in institute to function as ultraviolet absorbing agent
328.Ultraviolet light can be effectively absorbed, it has been used for polyethylene, polypropylene, polyphenyl second as a kind of important ultraviolet absorbing agent
Alkene, polyvinyl chloride, polyester, epoxy resin, ABS resin and celluosic resin etc. are in the coating of matrix, in various coating
With excellent light stablizing effect.
When synthesizing 2- (bis- tertiary amyl phenyl of 2'- hydroxyl -3', 5'-) benzotriazole, following steps are generallyd use: step
1, ortho-nitraniline and nitrous acid (under strong acid media) generate diazonium salt through diazo-reaction；Step 2, the diazonium salt and 2,
Bis- tert-amyl phenol of 4- carries out coupling reaction synthetic intermediate azo product；Step 3, intermediate azo product use strong reductant
It is restored closed loop and obtains target product.Although the synthetic route raw material is easy to get, easy to operate, have the following disadvantages:
(1) it need to be reacted under strong acid media in the step 1, the damage to consersion unit is larger, required at high cost；
(2) azo double bond is directly reduced by amine using strong reductant in step 3, increases the generation of impurity.
(3) yield is lower, and the difficult point of synthesis is that the intermediate azo product of the step 3 obtains mesh through restoring closed loop
Mark the synthesis process of product.
Current most of manufacturing enterprises produce 2- (bis- tertiary amyl phenyl of 2'- hydroxyl -3', 5'-) benzene using this synthetic route
And triazole product, the difference of the solvent and catalyst that are used in the synthesis process due to reduction closed loop procedure, obtained product matter
Amount, yield, cost are each has something to recommend him, and different degrees of pollution is caused to environment.
Summary of the invention
It is an object of the invention to solve the problems, such as that yield existing in the prior art is low, at high cost and environmental pollution, mention
For a kind of high income, purity is high, at low cost, production process safety, 2- (bis- tertiary amyl of 2'- hydroxyl -3', 5'- of three wastes low emission
Phenyl) benzotriazole process synthetic method.
The present invention is implemented as follows:
The present invention provides the preparation methods of ultraviolet absorbing agent UV-328 a kind of comprising following steps:
The preparation of steps 1 and 2-nitroaniline: 2- nitro-chlorobenzene and ammonium hydroxide are squeezed into and carry out aminating reaction in ammoniation reactor
Afterwards, layering is stood, and after cooling crystallization, obtains 2- nitroaniline product；Wherein the concentration of the ammonium hydroxide is 10%~25%, described
The molar ratio of 2- nitro-chlorobenzene and ammonium hydroxide is 1:12~22；
The preparation of step 2,2- nitro benzene diazonium hydrochloride: by 2- nitroaniline, hydrochloric acid, being added diazo-reaction kettle,
Stirring is cooled to 10 DEG C and hereinafter, NaNO is added2Aqueous solution after insulation reaction, is added urea and terminates reaction, filtering, gained filter
Liquid is 2- nitro benzene diazonium HCI solution；Wherein the mass fraction of the hydrochloric acid is 5%~35%, the NaNO2Water
The mass fraction of solution is 5%~35%；
Step 3,2- nitro -2 '-hydroxyl -3 ', the preparation of 5 '-two tertiary amyl azobenzenes: by bis- tert-amyl phenol of 2,4-, alcohol
Substance is added in coupling reaction kettle, stirring and dissolving, is cooled to 10 DEG C and hereinafter, adjusts PH, the resulting 2- of temperature control a dropping step 2
Nitro benzene diazonium HCI solution, coupling reaction is filtered to complete, is washed, dry, obtain 2- nitro -2 '-hydroxyl -3 ', 5 ' -
Two tertiary amyl azobenzenes；Wherein alcohols material used in step 3 is dehydrated alcohol；
The preparation of step 4,2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides: by 2- nitro -
2 '-hydroxyls -3 ', 5 '-two tertiary amyl azobenzenes, reducing agent, alkaline matter are added in a step reduction reaction kettle, it is warming up to reflux,
Carrying out reduction reaction a to reaction terminates, cooling, adjusts PH 1~5, filtering, filter cake is washed with water, drains, and filter cake is
2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides；The reducing agent is methanol, in isopropanol, formaldehyde
At least one, -2 '-hydroxyl -3 of 2- nitro ', 5 '-two tertiary amyl azobenzenes, reducing agent, alkaline matter molar ratio be
1:8~12:0.2~0.8；
The preparation of step 5,2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole: by 2- (2'- hydroxyl -3 ',
5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides, 20%~35% hydrochloric acid, zinc powder and toluene is added in two step reduction kettles, rises
Temperature is to flowing back, until reaction terminates, filtering removal zinc powder, filtrate water washing, cooling crystallization, filtering, filter cake ethyl acetate into
Row recrystallization processing, filtering, filtrate recycling ethyl acetate apply, obtained after filtration cakes torrefaction 2- (2'- hydroxyl -3 ', 5 '-two spies penta
Base phenyl) benzotriazole product；The 2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides, hydrochloric acid,
Zinc powder, the molal volume ratio of toluene are 1mol:2.5~3mol:0.05~0.2mol:800~1200mL.
Preferably, in the step 1, aminating reaction carries out under 150~220 DEG C, 12~20MPa, aminating reaction when
Between be 30~50min.
Preferably, in the step 1, by NH remaining in system3It is absorbed through water and generates low concentration ammonium hydroxide, then add portion
Continue after liquid separation ammonia for aminating reaction；The material of deamination is layered, stand after ammonium chloride obtained in limewash with recycling
NH3It is applied.The byproduct ammonium hydroxide of comprehensive utilization company existing procucts and it is made to obtain scale application.
Preferably, in the step 2, the insulation reaction time is 30min~90min.
Preferably, 2- nitroaniline, hydrochloric acid, NaNO described in the step 22Molar ratio be 1:3~4:1~2.
Preferably, in the step 3, the molal volume ratio of 2,4- bis- tert-amyl phenols and alcohols material is 1mol:1L.
Preferably, in the step 3, adjust PH when use mass fraction for 6%~18% alkaline substance solution；Institute
The time for stating coupling reaction is 2~6h.
Preferably, the time of a reduction reaction is 6~12h in the step 4；It is cooled to 25~35 after reaction
DEG C, PH is adjusted 1~5 with 20%~35% hydrochloric acid.
Preferably, in the step 4, -2 '-hydroxyl -3 of 2- nitro ', 5 '-two tertiary amyl azobenzenes, reducing agent, alkali
Property substance optimum mole ratio be 1:10:0.5.
Preferably, in the step 4, the reducing agent is the mixture of isopropanol, formaldehyde, and isopropanol, formaldehyde rub
You are than being 6~8:1.Most preferably, the reducing agent is isopropanol, the mixture of formaldehyde, and the molar ratio of isopropanol, formaldehyde
For 7:1.
Preferably, 2- described in the step 5 (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides,
Hydrochloric acid, zinc powder, the optimum molar volume ratio of toluene are 1mol:2.9mol:0.1mol:1L.
The invention has the advantages that:
1, the preparation method of a kind of ultraviolet absorbing agent UV-328 provided by the invention, a large amount of innovative spies through the application
Rope has developed the production method using low concentration ammonium hydroxide prepare with scale 2- nitroaniline: 2- nitro-chlorobenzene use concentration for
Again with nitrous acid through diazonium after 10%~25% ammonium hydroxide ammonification (and the molar ratio of 2- nitro-chlorobenzene and ammonium hydroxide is 1:12~22)
Change reaction and generate diazonium salt, which fully utilizes our company's existing procucts without carrying out under strong acid media
Byproduct ammonium hydroxide, three wastes low emission, and required at low cost.
2, the preparation method of ultraviolet absorbing agent UV-328 provided by the invention a kind of, the reduction of intermediate azo product are closed
Ring process uses 2 stage reduction methods: (1) being made in first step reduction reaction using methanol, isopropanol or formaldehyde with week reduction
For reducing agent by 2- nitro -2 '-hydroxyl -3 ', 5 '-two tertiary amyl azobenzenes be reduced to 2- (2 '-hydroxyls -3 ', 5 '-two tertiary amyls
Phenyl) benzotriazole nitrogen oxides, it avoids strong reductant and azo double bond is directly reduced into amine, reduce impurity and generate；(2)
Using the method for zinc powder is added in an acidic solution by 2- (2 '-hydroxyls -3 ', 5 '-two tertiary amyl phenyl) in two step reduction reactions
Benzotriazole nitrogen oxides is reduced to 2- (2 '-hydroxyls -3 ', 5 '-two tertiary amyl phenyl) benzotriazole product for the second time, and zinc powder returns
Rear enclosure is received to use；Finally make solvent using ethyl acetate in the final purification process of product and removes impurity in product.2 step reduction
Method, which not only increases product purity, reduces the generation of impurity, while improving product yield, and catalyst, the solvent etc. used
It not can cause environmental pollution.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the preparation method of ultraviolet absorbing agent UV-328 provided by the invention；
Fig. 2 is a kind of chemical equation of the preparation method of ultraviolet absorbing agent UV-328 provided by the invention.
Specific embodiment
Embodiment 1
The present invention through ammonification, diazotising, coupling, step reduction, two step reduction reactions and was post-processed by o-nitrochlorobenzene
Journey prepares 2- (bis- tertiary amyl phenyl of 2'- hydroxyl -3', 5'-) benzotriazole product.
The preparation of steps 1 and 2-nitroaniline: 20% ammonium hydroxide of the 2- nitro-chlorobenzene of 1mol and 20mol is squeezed into duct type
Interior aminating reaction 30~50 minutes under 150~220 DEG C, 12~20MPa of ammoniation reactor carry out ammonia remaining in system through injection
The low concentration ammonium hydroxide that cyclic absorption generates, continues after adding part liquefied ammonia for aminating reaction, the material of deamination is layered, static
It (is applied in limewash with recycling ammonia) after point removing ammonium chloride, obtains 2- nitroaniline product through cooling crystallization, yield >=
98.6%, purity >=99.6%.
The preparation of step 2,2- nitro benzene diazonium hydrochloride: by the 2- nitroaniline of 1mol, 31% salt of 3.2mol
Diazo-reaction kettle is added in the water of acid and 500ml, and stirring is cooled to 10 DEG C hereinafter, 30% NaNO of 1.1mol is added2It is water-soluble
Liquid, insulation reaction 60min are added a small amount of urea and terminate reaction, and filtering, gained filtrate is that 2- nitro benzene diazonium hydrochloride is molten
Liquid.
Step 3,2- nitro -2 '-hydroxyl -3 ', the preparation of 5 '-two tertiary amyl azobenzenes: by bis- tertiary amyl of 2,4- of 1mol
Phenol, 1000ml alcohols material be added coupling reaction kettle in, stirring and dissolving is cooled to 10 DEG C hereinafter, with 15% alkaline matter
Aqueous solution adjusts PH to alkalescent (preferably 7.2-7.8), and 2- nitro benzene diazonium HCI solution is added dropwise in temperature control, and reaction 3 is small
When, filter, wash filter cake with a small amount of alcohols material, it is dry, obtain 2- nitro -2 '-hydroxyl -3 ', 5 '-two tertiary amyl azobenzenes, receipts
Rate >=94%, purity >=98%.
The preparation of step 4,2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides: by the 2- of 1mol
Nitro -2 '-hydroxyl -3 ', 5 '-two tertiary amyl azobenzenes, 10mol reducing agent (reducing agent be isopropanol, formaldehyde mixing
Object, and the molar ratio of isopropanol, formaldehyde is 7:1), 0.5mol sodium hydroxide is added in a step reduction reaction kettle, is warming up to reflux,
Terminate to reaction within reaction about 6~12 hours, 25 DEG C~35 DEG C of cooling adjusts PH 3~4 with 30% hydrochloric acid, filters, filter cake water
Washing, is drained, and filter cake is 2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides.
The preparation of step 5,2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole: by 2- (the 2'- hydroxyl of 1mol
Base -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides, 30% hydrochloric acid 2.9mol, 0.1mol zinc powder and toluene 1000ml
It is added in two step reduction kettles, is warming up to reflux, terminate to reaction within reaction 2~6 hours, filtering removal zinc powder, filtrate water washs
To center, cooling crystallization is filtered, and filter cake carries out recrystallization processing with ethyl acetate, is filtered, and filtrate recycling ethyl acetate is applied,
2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole product is obtained after filtration cakes torrefaction.To 2- nitro -2 '-hydroxyl -3 ',
5 '-two tertiary amyl azobenzenes calculate total recovery >=88.8% of two steps reduction, product purity >=99.5%.
Embodiment 2
The present invention through ammonification, diazotising, coupling, step reduction, two step reduction reactions and was post-processed by o-nitrochlorobenzene
Journey prepares 2- (bis- tertiary amyl phenyl of 2'- hydroxyl -3', 5'-) benzotriazole product.
The preparation of steps 1 and 2-nitroaniline: 10% ammonium hydroxide of the 2- nitro-chlorobenzene of 1mol and 22mol is squeezed into duct type
Interior aminating reaction 30~50 minutes under 150~220 DEG C, 12~20MPa of ammoniation reactor carry out ammonia remaining in system through injection
The low concentration ammonium hydroxide that cyclic absorption generates, continues after adding part liquefied ammonia for aminating reaction, the material of deamination is layered, static
It (is applied in limewash with recycling ammonia) after point removing ammonium chloride, obtains 2- nitroaniline product through cooling crystallization, yield >=
98.3%, purity >=99.2%.
The preparation of step 2,2- nitro benzene diazonium hydrochloride: by the 2- nitroaniline of 1mol, 3mol 5% hydrochloric acid and
Diazo-reaction kettle is added in the water of 500ml, and stirring is cooled to 10 DEG C hereinafter, 5% NaNO of 1.2mol is added2Aqueous solution is protected
Temperature reaction 60min is added a small amount of urea and terminates reaction, and filtering, gained filtrate is 2- nitro benzene diazonium HCI solution.
Step 3,2- nitro -2 '-hydroxyl -3 ', the preparation of 5 '-two tertiary amyl azobenzenes: by bis- tertiary amyl of 2,4- of 1mol
Phenol, 1000ml alcohols material be added coupling reaction kettle in, stirring and dissolving is cooled to 10 DEG C hereinafter, with 6% alkaline matter water
Solution adjusts PH to alkalescent (preferably 7.2-7.8), and 2- nitro benzene diazonium HCI solution is added dropwise in temperature control, reacts 3 hours,
Filter, wash filter cake with a small amount of alcohols material, dry, obtain 2- nitro -2 '-hydroxyl -3 ', 5 '-two tertiary amyl azobenzenes, yield >=
94%, purity >=98%.
The preparation of step 4,2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides: by the 2- of 1mol
Nitro -2 '-hydroxyl -3 ', a step reduction reaction kettle is added in 5 '-two tertiary amyl azobenzenes, the methanol of 8mol, 0.2mol sodium hydroxide
In, it is warming up to reflux, is terminated to reaction within reaction about 6~12 hours, 25 DEG C~35 DEG C cooling, adjusting PH with 20% hydrochloric acid is 1, mistake
Filter, filter cake is washed with water, drains, and filter cake is 2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides.
The preparation of step 5,2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole: by 2- (the 2'- hydroxyl of 1mol
Base -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides, 20% hydrochloric acid 2.5mol, 0.05mol zinc powder and toluene 800ml
It is added in two step reduction kettles, is warming up to reflux, terminate to reaction within reaction 2~6 hours, filtering removal zinc powder, filtrate water washs
To center, cooling crystallization is filtered, and filter cake carries out recrystallization processing with ethyl acetate, is filtered, and filtrate recycling ethyl acetate is applied,
2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole product is obtained after filtration cakes torrefaction.To 2- nitro -2 '-hydroxyl -3 ',
5 '-two tertiary amyl azobenzenes calculate total recovery >=88.1% of two steps reduction, product purity >=99.2%.
Embodiment 3
The present invention through ammonification, diazotising, coupling, step reduction, two step reduction reactions and was post-processed by o-nitrochlorobenzene
Journey prepares 2- (bis- tertiary amyl phenyl of 2'- hydroxyl -3', 5'-) benzotriazole product.
The preparation of steps 1 and 2-nitroaniline: 25% ammonium hydroxide of the 2- nitro-chlorobenzene of 1mol and 12mol is squeezed into duct type
Interior aminating reaction 30~50 minutes under 150~220 DEG C, 12~20MPa of ammoniation reactor carry out ammonia remaining in system through injection
The low concentration ammonium hydroxide that cyclic absorption generates, continues after adding part liquefied ammonia for aminating reaction, the material of deamination is layered, static
It (is applied in limewash with recycling ammonia) after point removing ammonium chloride, obtains 2- nitroaniline product through cooling crystallization, yield >=
98.2%, purity >=99.5%.
The preparation of step 2,2- nitro benzene diazonium hydrochloride: by the 2- nitroaniline of 1mol, 35% hydrochloric acid of 4mol
And diazo-reaction kettle is added in the water of 500ml, stirring is cooled to 10 DEG C hereinafter, 35% NaNO of 1.2mol is added2Aqueous solution,
Insulation reaction 60min is added a small amount of urea and terminates reaction, and filtering, gained filtrate is 2- nitro benzene diazonium HCI solution.
Step 3,2- nitro -2 '-hydroxyl -3 ', the preparation of 5 '-two tertiary amyl azobenzenes: by bis- tertiary amyl of 2,4- of 1mol
Phenol, 1000ml ethyl alcohol be added coupling reaction kettle in, stirring and dissolving is cooled to 10 DEG C hereinafter, water-soluble with 18% sodium hydroxide
Liquid adjusts PH to alkalescent (preferably 7.2-7.8), and 2- nitro benzene diazonium HCI solution is added dropwise in temperature control, reacts 3 hours, takes out
Filter, it is dry with a small amount of ethanol washing filter cake, obtain 2- nitro -2 '-hydroxyl -3 ', 5 '-two tertiary amyl azobenzenes, yield >=94%,
Purity >=98%.
The preparation of step 4,2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides: by the 2- of 1mol
Nitro -2 '-hydroxyl -3 ', it is anti-that step reduction is added in 5 '-two tertiary amyl azobenzenes, the isopropanol of 12mol, 0.8mol sodium hydroxide
It answers in kettle, is warming up to reflux, terminate to reaction within reaction about 6~12 hours, 25 DEG C~35 DEG C of cooling adjusts PH with 35% hydrochloric acid and exists
5, filtering, filter cake is washed with water, drains, and filter cake is 2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxidation
Object.
The preparation of step 5,2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole: by 2- (the 2'- hydroxyl of 1mol
Base -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides, 35% hydrochloric acid 3.0mol, 0.2mol zinc powder and toluene 1200ml
It is added in two step reduction kettles, is warming up to reflux, terminate to reaction within reaction 2~6 hours, filtering removal zinc powder, filtrate water washs
To center, cooling crystallization is filtered, and filter cake carries out recrystallization processing with ethyl acetate, is filtered, and filtrate recycling ethyl acetate is applied,
2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole product is obtained after filtration cakes torrefaction.To 2- nitro -2 '-hydroxyl -3 ',
5 '-two tertiary amyl azobenzenes calculate total recovery >=88.2% of two steps reduction, product purity >=99.3%.
Comparative example 1
Step 1- step 3 is with embodiment 1, the difference is that step 4 and step 5, which are replaced with strong reductant, carries out a step reduction
Reaction, yield >=68.5% of reduction, product purity >=63.7%.
Experimental example 1
1, exothermic process when due to aminating reaction, it is low that excessively high reaction density will lead to heat release difficulty yield；Too low is anti-
It answers concentration yield low or even is difficult to be reacted, therefore it is most important to explore suitable ammonia concn.The applicant explores
The ammonium hydroxide of various concentration prepare 2- nitroaniline (other reaction conditions are identical: the molar ratio of 2- nitro-chlorobenzene and ammonium hydroxide be 1:20,
Interior aminating reaction 30~50 minutes under 150~220 DEG C, 12~20MPa of duct type ammoniation reactor), and calculate various concentration
Under yield, as shown in table 1.
Table 1
| Group | Ammonia concn (mass fraction) | Yield |
| 1 | 5% | 28.6% |
| 2 | 10% | 81.2% |
| 3 | 15% | 99.2% |
| 4 | 20% | 99.6% |
| 5 | 25% | 99.5% |
| 6 | 30% | 56.7% |
| 7 | 35% | 38.5% |
| 8 | 40% | 32.6% |
As shown in Table 1, ammonia concn is lower than 10%, and yield is low；Ammonia concn is also low higher than 25% yield；Therefore this Shen
Concentration please be use to be reacted for 10%~25% ammonium hydroxide.
2, suitable reaction molar ratio is explored
The applicant explores 2- nitro-chlorobenzene, and (other reaction conditions are identical: ammonium hydroxide with the different mol ratio of ammonium hydroxide
Concentration is 20%, interior aminating reaction 30~50 minutes under 150~220 DEG C, 12~20MPa of duct type ammoniation reactor), and count
The yield under various concentration is calculated, as shown in table 2.
Table 2
| Group | The molar ratio of 2- nitro-chlorobenzene and ammonium hydroxide | Yield |
| 1 | 1:5 | 32.6% |
| 2 | 1:10 | 61.3% |
| 3 | 1:12 | 98.5% |
| 4 | 1:15 | 99.1% |
| 5 | 1:20 | 99.6% |
| 6 | 1:22 | 98.8% |
| 7 | 1:25 | 54.6% |
| 8 | 1:30 | 36.1% |
As shown in Table 2, the molar ratio of 2- nitro-chlorobenzene and ammonium hydroxide described in the step 1 is 1:12~22, and yield is higher.
Experimental example 2
1, comparative example 1 will increase impurity, lead to product purity it is found that azo double bond is directly reduced into amine by strong reductant
It is low.
2, in the step 4, -2 '-hydroxyl -3 of 2- nitro ', 5 '-two tertiary amyl azobenzenes, reducing agent, alkaline matter
Appropriate molar ratios exploration.Only above-mentioned molar ratio is different outer, and other conditions are the same as embodiment 1.Some experimental data is listed below
As shown in table 3.
Table 3
As shown in Table 3, -2 '-hydroxyl -3 of 2- nitro ', 5 '-two tertiary amyl azobenzenes, reducing agent, alkaline matter rub
When you are than being 1:8~12:0.2~0.8, purity is high, high income.And in the step 4, -2 '-hydroxyl -3 of 2- nitro ',
5 '-two tertiary amyl azobenzenes, reducing agent, alkaline matter optimum mole ratio be 1:10:0.5.
3, in the step 5, hydrochloric acid, zinc powder, the exploration of the molal volume ratio of toluene.Only above-mentioned molal volume is than different
Outside, other conditions are the same as embodiment 1.It is as shown in table 4 that some experimental data is listed below.
Table 4
As shown in Table 4, described；The 2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides, salt
Acid, zinc powder, when the molal volume ratio of toluene is 1mol:2.5~3mol:0.05~0.2mol:800~1200mL, purity is high is received
Rate is high.And 2- described in the step 5 (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides, hydrochloric acid, zinc
Powder, the optimum molar volume ratio of toluene are 1mol:2.9mol:0.1mol:1L.
Through the foregoing embodiment, it will thus be seen that
(1) preparation method of a kind of ultraviolet absorbing agent UV-328 provided by the invention, the reduction of intermediate azo product
Closed loop procedure uses 2 stage reduction methods: avoiding strong reductant and azo double bond is directly reduced into amine, reduce impurity and generate, not only
Product purity is improved, while improving product yield.
(2) preparation method of a kind of ultraviolet absorbing agent UV-328 provided by the invention, a large amount of novelties through the application
Explore and have developed production method using low concentration ammonium hydroxide prepare with scale 2- nitroaniline: 2- nitro-chlorobenzene use concentration for
Again with nitrite through weight after 10%~25% ammonium hydroxide ammonification (and the molar ratio of 2- nitro-chlorobenzene and ammonium hydroxide is 1:12~22)
Nitridation reaction generates diazonium salt, which fully utilizes our company and have production without carrying out under strong acid media
The byproduct ammonium hydroxide of product, three wastes low emission, and it is required at low cost.
Experimental example 3
1, for the exploration of weak reductant used by first step reduction reaction
It is grouped by table 5, is all made of total reducing agent of 10mol, (the tool in addition to the ingredient of reducing agent in step 4 is different
5) body is shown in Table, remaining is the same as embodiment 1.After the completion of one step reduction reaction, HPLC testing product purity.
Table 5
| Group | Reducing agent | Purity |
| 1 | Isopropanol, formaldehyde molar ratio be 5:1 | 81.2% |
| 2 | Isopropanol, formaldehyde molar ratio be 6:1 | 95.6% |
| 3 | Isopropanol, formaldehyde molar ratio be 7:1 | 99.4% |
| 4 | Isopropanol, formaldehyde molar ratio be 8:1 | 96.1% |
| 5 | Isopropanol, formaldehyde molar ratio be 9:1 | 79.3% |
| 6 | Methanol, formaldehyde molar ratio be 8:1 | 85.5% |
| 7 | Formaldehyde | 82.4% |
| 8 | Methanol | 78.3% |
| 9 | Isopropanol | 68.7% |
| 10 | Methanol, isopropanol molar ratio be 8:1 | 72.5% |
In first step reduction reaction using methanol, isopropanol or formaldehyde with week reduction as reducing agent by 2- nitre
Base -2'- hydroxyl -5'- spy's octyl azobenzene is reduced to 2- (2 '-hydroxyls -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxidation
Object avoids strong reductant and azo double bond is directly reduced into amine, reduces impurity and generates.As shown in Table 5, wherein preferably, institute
The mixture that reducing agent is isopropanol, formaldehyde is stated, and the molar ratio of isopropanol, formaldehyde is 6~8:1.Most preferably, isopropyl
Alcohol, formaldehyde molar ratio be 7:1.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of ultraviolet absorbing agent UV-328, which is characterized in that it includes the following steps:
The preparation of steps 1 and 2-nitroaniline: 2- nitro-chlorobenzene and ammonium hydroxide being squeezed into ammoniation reactor after carrying out aminating reaction,
Layering is stood, and after cooling crystallization, obtains 2- nitroaniline product；Wherein the concentration of the ammonium hydroxide is 10%~25%, the 2-
The molar ratio of nitro-chlorobenzene and ammonium hydroxide is 1:12~22；
The preparation of step 2,2- nitro benzene diazonium hydrochloride: by 2- nitroaniline, hydrochloric acid, diazo-reaction kettle, stirring is added
It is cooled to 10 DEG C and hereinafter, NaNO is added2Aqueous solution after insulation reaction, is added urea and terminates reaction, filtering, gained filtrate is
For 2- nitro benzene diazonium HCI solution；Wherein the mass fraction of the hydrochloric acid is 5%~35%, the NaNO2Aqueous solution
Mass fraction be 5%~35%；
Step 3,2- nitro -2 '-hydroxyl -3 ', the preparation of 5 '-two tertiary amyl azobenzenes: by bis- tert-amyl phenol of 2,4-, alcohols object
Matter is added in coupling reaction kettle, stirring and dissolving, is cooled to 10 DEG C and hereinafter, adjusts PH, the resulting 2- nitro of temperature control a dropping step 2
Benzene diazonium HCI solution, coupling reaction is filtered to complete, is washed, dry, obtain 2- nitro -2 '-hydroxyl -3 ', 5 '-two is special
Amyl azobenzene；
The preparation of step 4,2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides: by 2- nitro -2 '-hydroxyl
Base -3 ', 5 '-two tertiary amyl azobenzenes, reducing agent, alkaline matter are added in a step reduction reaction kettle, are warming up to reflux, carry out one
Secondary reduction reaction to reaction terminates, cooling, adjusts PH 1~5, filtering, filter cake is washed with water, drains, and filter cake is 2- (2'-
Hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides；The reducing agent be methanol, isopropanol, in formaldehyde at least
One kind, -2 '-hydroxyl -3 of 2- nitro ', 5 '-two tertiary amyl azobenzenes, reducing agent, alkaline matter molar ratio be 1:8~
12:0.2~0.8；
The preparation of step 5,2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole: by 2- (2'- hydroxyl -3 ', 5 '-two
Tertiary amyl phenyl) benzotriazole nitrogen oxides, 20%~35% hydrochloric acid, zinc powder and toluene is added in two step reduction kettles, is warming up to
Reflux, until reaction terminates, filtering removal zinc powder, filtrate water is washed, cooling crystallization, filtering, and filter cake carries out weight with ethyl acetate
Crystallization treatment, filtering, filtrate recycling ethyl acetate apply, obtained after filtration cakes torrefaction 2- (2'- hydroxyl -3 ', 5 '-two tert-amylbenzenes
Base) benzotriazole product；The 2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides, hydrochloric acid, zinc powder,
The molal volume ratio of toluene is 1mol:2.5~3mol:0.05~0.2mol:800~1200mL.
2. the preparation method of ultraviolet absorbing agent UV-328 as described in claim 1, which is characterized in that in the step 1, ammonia
Change reacts on 150~220 DEG C, carries out under 12~20MPa, and the time of aminating reaction is 30~50min.
3. the preparation method of ultraviolet absorbing agent UV-328 as described in claim 1, which is characterized in that, will in the step 1
Remaining NH in system3It is absorbed through water and generates low concentration ammonium hydroxide, continued after then adding part liquefied ammonia for aminating reaction；Deamination
Material it is layered, stand after ammonium chloride in limewash and recycling obtains NH3It is applied.
4. the preparation method of ultraviolet absorbing agent UV-328 as described in claim 1, which is characterized in that in the step 2, protect
The warm reaction time is 30min~90min.
5. the preparation method of ultraviolet absorbing agent UV-328 as described in claim 1, which is characterized in that institute in the step 2
State 2- nitroaniline, hydrochloric acid, NaNO2Molar ratio be 1:3~4:1~2.
6. the preparation method of ultraviolet absorbing agent UV-328 as described in claim 1, which is characterized in that in the step 3,2,
The molal volume ratio of bis- tert-amyl phenol of 4- and alcohols material is 1mol:1L.
7. the preparation method of ultraviolet absorbing agent UV-328 as described in claim 1, which is characterized in that in the step 3, adjust
Save PH when use mass fraction for 6%~18% alkaline substance solution；The time of the coupling reaction is 2~6h.
8. the preparation method of ultraviolet absorbing agent UV-328 as described in claim 1, which is characterized in that one in the step 4
The time of secondary reduction reaction is 6~12h；Be cooled to 25~35 DEG C after reaction, with 20%~35% hydrochloric acid adjust PH 1~
5。
9. the preparation method of ultraviolet absorbing agent UV-328 as described in claim 1, which is characterized in that in the step 4, institute
State 2- nitro -2 '-hydroxyl -3 ', 5 '-two tertiary amyl azobenzenes, reducing agent, alkaline matter molar ratio be 1:10:0.5；It is described
Reducing agent described in step 4 is the mixture of isopropanol, formaldehyde, and the molar ratio of isopropanol, formaldehyde is 6~8:1.
10. the preparation method of ultraviolet absorbing agent UV-328 as described in claim 1, which is characterized in that institute in the step 5
2- (2'- hydroxyl -3 ', 5 '-two tertiary amyl phenyl) benzotriazole nitrogen oxides is stated, the molal volume ratio of hydrochloric acid, zinc powder, toluene is
1mol:2.9mol:0.1mol:1L.
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| CN106083749A (en) * | 2016-05-31 | 2016-11-09 | 启东金美化学有限公司 | A kind of preparation method of Benzotriazole Ultraviolet Stabilizer |
| CN108148009A (en) * | 2017-12-29 | 2018-06-12 | 天津利安隆新材料股份有限公司 | A kind of method that Benzotriazole Ultraviolet Stabilizer is prepared using catalytic hydrogen transfer method |
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| CN105602009A (en) * | 2016-02-17 | 2016-05-25 | 黄秀茹 | Additive used for polymer and additive composition and polymer composition thereof |
| CN106083749A (en) * | 2016-05-31 | 2016-11-09 | 启东金美化学有限公司 | A kind of preparation method of Benzotriazole Ultraviolet Stabilizer |
| CN108148009A (en) * | 2017-12-29 | 2018-06-12 | 天津利安隆新材料股份有限公司 | A kind of method that Benzotriazole Ultraviolet Stabilizer is prepared using catalytic hydrogen transfer method |
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